Emulsion



Patented July 11, 1933 UNITED STATES PATENT OFFICE EMULSION No Drawing.Application filed September 11., 1980, Serial No. 481,348. RenewedOctober 5, 1982.

My invention relates in general to improved emulsions and emulsionimproving substances. It relates more specifically to an improvednon-spattering type of margarine and anti-spattering substances for usewith margarine.

By means of my new products I am able to impartsuperior qualities tomany types of emulsions, particularly emulsions of fats and oils usedfor culinary purposes, but I shall explain the same in connection withimprovements in margarine. Those skilled in the art are referred to myprior application Serial Number 383,143, filed on August 2, 1929, for amore complete disclosure of certain details of the invention than ismade herein. I wish also to call attention to my co-pending applicationSerial Number 475,622, filed on Aug. 15, 1930, as a continuation in partof application Serial Number 383,143, filed August 2, 1929.

In general the present invention represents a specific embodiment of themain invention disclosed in the co-pending application above referredto, and while the present disclosure is substantially complete in so faras it describes the invention and supports the claims, those interestedin the art are referred to the co-pending case for a more completedisclosure of the basic concept of the invention. The principal objectof my .present invention is to improve such forms of emulsions asmargarine.

Another object is to reduce the spattering of margarine when used forfrying purposes and generally improve its frying behavior.

Other objects and features of the invention will be apparent from aconsideration of the following detailed description.

As was disclose in my prior applications I have discovered a large classof chemical compounds which may be used to impart improvedcharacteristics to all types of wateroil emulsions, particularly thoseused for cooking purposes, and other types of culinary fat preparations.These substances have several characteristics in common which make themvery valuable in their use with margarine. These substances arecompatible 0 with mild acids and in particular with lactic acid in theconcentration and under the conditions existing in margarine. The aredifficultly soluble in oils and fats an aqueous media and in many casesare substantially insoluble. This makes it possible to use these comounds in very small quantities, as they may considered to concentrate atthe water-oil interface of the emulsion rather than be dissolved ineither the water or oil phase. These substances are semi-colloidal ortruly colloidal in character and are frequently colloidally dispersiblein aqueous and/or oleaginous media. They are, moreover, substantiallynon-volatile at margarine frying temperatures and so will remain in themargarine and perform their function during rying.

One of the most important characteristics of these compounds is thepresence in the molecule of two types of groups in balanced relation toeach other, one'group being bydrophyllic or water wetting in character,and the other group being lipophyllic or fat wetting in character. Thesegrou s must exist in the molecule in such a state 0 balance that theywill function at the water-oilinterface in the intended manner.Presumably these substances orientate themselves at the wateroilinterface, by reason of the balance of the two types of groups, but itis understood that 30 the invention does not depend upon thisexplanation.

My prior application treats exhaustively of the manner in which thebalance between the two groups may be determinedso that without tests ofany kind it is possible for the skilled colloid chemist to pick outcompounds which can not function efl'ectivel as anti-spatterers, as wellas compounds w chclearly will be effective as anti-spatterers.

However, there are compounds'of such character that the state of balanceexisting between the two rou s in the molecule is preferably determineda sim le quick test.

The balance of the ydrop ile-lipophile .5 groups in the compound which Iapply in my invention is one of the characteristics and determinant ofthe class of substanws which I employ.

The test which I have chosen as a means m for determining thehydrophile-lipophile balance in organic compounds, I call the spoontest. It is carried out as follows: From 0.05 to 0.10 gr. of thematerial or substance in question is introduced'into a porcelain mortar,wetted and ground into a smooth paste with a pestle with a minimumproportion of water; two to five drops generally will suiiice.

An ordinary margarine such for example as one made fromvegetable oils,and fats and cultured skimmed milk and which possesses the usualproperty of spattering during frying is selected. Ten grams of thismargarineare then introduced in small portions into the mortar andmacerated thoroughly with the paste first prepared until the entire tengram portion is thoroughly and uniformly intermixed with the material inthe mortar. Two grams of thismixture are introduced into a tablespoonand'held directly over a free flame, such for example a Bunsen flame,one or two inches long, in such a position that the point of the flamejust about reaches the bottom of the spoon. A clean sheet of paper isplaced on the bottom of the burner by inserting the stem of the Bunsenburner prior to lighting through a hole made in the center of the paperand allowing the paper to drop to the base of the burner to catch themargarine splashed out during the heating. The mixture in the spoon isheated until all of the water is boiled off and ebullition ceases andthe spots on the paper observed.

If this treated margarine spots the paper to the same extent as theuntreated margarine from which the former was prepared, then thelipophile and hydrophile groups of the compound are not balanced. Thenumber and size of spots on the paper or the added weight can be readilydetermined.

If the increase in weight of the paper or the number and character ofthe spots produced on the paper up until all the water has boiled oilare less than that produced by similarly heating two grams of theoriginal untreated margarine employed for the test, then the material orsubstance in question has balanced hydrophile-lipophile groups. Theexpression balanced lipophile and hydrophile groups used in the claimsis to be interpreted in terms of the above described spoon test, and inthe light of the entire disclosure.

As will appear from my co -pending applications, it is not as a generalrule, advisable to employ nitrogenouscompounds as an antispatterer, eventhough their anti-spattering behavior may be very satisfactory. This isdue to the fact that many nitrogenous compounds are very apt to liberatefrom themselves when used in margarine and other types of emulsions,objectionable substances such as choline or other objectionable amines.I state for this reason in the co-pending application above set out,that I prefer to avoid the use of nitrogenous compounds. I have nowdiscovered that many nitrogenous compounds can be used with satisfactionproviding the nitrogenous compounds selected are of such a characterthat no objectionable taste and odor can in any way be develo ed duringconditions incident to the manu acture, storage, and use of margarine. Ihave found that if the molecular structure is devoid of the nitrogenouslinkage O-XO (CH N- (wherein O represents oxygen, X stands forphosphorous or sulphur, in the form of their oxygenated acid radicalssuch as phosphoric, sulphuric, etc., C represents carbon, H is hydrogen,w is a small whole number, and N is trivalent or pentavalent nitrogen,the terminal ox gen indicated being linked directly to car on) it issatisfactory for my purpose.

Examples of some of the nitrogenous substances which I have used asanti-spattering agents, many of them not known heretofore,

are as follows Palmityl glycine,

Stearyl creatinine, (sodium salt), Stearyl glutamic acid,

II I ll CnHu-C-NCHCHz-CH1COH Stearyl peptone, Palmityl leuclne,

o o con on, t A C 1Hu NH- n-cm-on-orn Cholesteryl ester of betainechloride,

p Cl CH: C11H15O-(E-CH7N-CH3 CH: 0 Cl CH3 CHI Melissyldimethyl-aminoacetate hydro bromide,

IO CH3 CH3 Palmityl ester of betaine chloride Cholesteryl ester ofbetaine chloride (Cargopahnitoxy) methyl pyridynium bro- Melissyl esterof betaine bromide Melissyl ester of betaine chloride(Carbocholesteroxy) methyl pyridinium bromide,

(Carbocholesteroxy) methyl dimethylphenyl-ammonium bromide Br(Carbocholesteroxy) methyl quinaldinium bromide CHI Br Cholesteryldimethyl-aminoacetate hydrobromide O CH] CH:

Palmityl ester of dimethylaminoacetic acid hydrobromide CH:ouna-o-t-cnr- -n r CH;

Stearyl glutamic acid,

t i clinu-d-nn cn-cnrcnr-c-on Palmito-leucine,

CHr-CO-NHCHz-COOH 1 a O-(Luri-cm-C-On spattering power 1s lacking. Thismatter is more fully discussed in my co-pending application, Serial No.383,143.

A general method for the preparation of the antispattering agents withwhich the present application is concerned is to dissolve or suspend thenitrogenous substance, freed of moisture, by drying or otherwise, in drypyridine, with heating if necessary, cooling this mixture, andintroducing into it the required amount of acyl chloride with agitation,either as such or dissolved in an inert solvent such as chloroform orcarbon tetrachloride, care being taken throughout to exclude moisture asfar as possible and to cool so as to control the heat of the reaction.The mixture protected from contact with atmospheric moisture, is thenallowed to stand at room temperature or is agitated at room temperaturefor six or eight hours or longer, and is then poured into iced dilutesulphuric acid, or some other acidulating agent. The product generallyseparates out, in the case of the acyl chloride of solid fatty acids, asa tie: cnlent solid. and in cases where acyl chlorides of liquid fattyacids have been used, generally speaking, as a liquid or semi-liquidmaterial.

It may then be washed several times with water or with brine, at roomtemperature or with the application of heat and finally separated fromthe water and dried.

In this procedure, other basic materials such as dimethyl aniline,quinoline, or quinaldinc may be substituted for the pyridine. Also, theacylation may be carried out in a different anhydrous medium or in anaqueous medium using a basic material such as calcium hydroxide orcarbonate to take care of the hydrochloric acid formed during the courseof the reaction.

The products may be purified, if desired, by recrystallizing fromsolvents.

Some of the anti-spattcrs of the class described herein which I preparedby the pyridine method are listed hereinbelow, with the proportions ofthe reacting materials used, indicated. The comparative anti-spatt-eringpowers of the fatty acid derivatives thus obtained are also shown. Theseanti-spattering powers were determined by the method described in fullin my co-pending application, Serial No. 383,143.

Hydrophyllic nitrogenous material Comparative apti-spattermg power Acylchloride Pyridine Fair Mode-rate (sodium salt) Very good Good Very goodlpart glycine 4 parts palmityl parts pyridine loride 3 pts stearyl chlore 2 parts glu- 4pts. stearyl chlotamie acid r 2 parts 1011- 3 4 pts.stearylchloride 1 part creat- 45 pts. pyridine inine pts. pyridine pts.pyridine cine 10 parts pop- 60 pts. pyridine ne (Merck's) I do not, ofcourse, limit my invention to the products obtained by using the abovelisted reagents in the proportions indicated, nor do I even limit myinvention to products obtained by the above described method, howeverthe proportions of the reagents may have been varied.

The scope of my invention includes compounds, however prepared, whensuch compounds comprise lipophile and hydrophile groups and when thehydrophile group contains nitrogen, in a linkage other than OXO(CH N- asherein described. Many other nitrogenous materials than those mentionedmay be utilized to furnish the hydrophile function, for example,alanine, phenylalanine, tyrosine, tryptophane, arginine, other aminoacids, and other nitrogenous substances with marked atlinity for water.

Many other materials than those mentioned may be utilized as sources oflipophile groups, for example: melissic acid, oleic acid, lauric acid,lauryl alcohol, palmityl alcohol, higher molecular weight esters andother substances with marked aflinity for oils and fats, as pointed outmore fully in my co-pending application, Serial No. 383,143.

I may, for example, hydrolize a protein down to the amino acid stage bythe use of a strong mineral acid or otherwise, then neutralize and drythe mixture and acetylate' more or less by the general method describedherein with the acyl chloride of a higher molecular weight fatty acid.

There are also many special methods available. Stearyl glycine, forexample. may be prepared by heating together stcaramide withcholoracetic acid or with sodium chloracetate.

The nitrogenous substances of my invention may be represented by theformula L('iR wherein "C and O are carbon and oxygen respectively, L isthe lipophile radical in the form of an alkyl or alkoxy group, or aderivative of an alkyl or alkoxy group and R represents the balancingnitrogenous hydrophile group. As pointed out previously herein, thisgroup is to be devoid of a certain linkage which I have foundobjectionable. More specifically and with specific classes of compoundsin mind my snb stances may be represented by the formula 0 cm-(cmm-t nwherein R" represents an amino acid radical devoid of the objectionablelinkage referred to. \Vith reference to the betaine series, I mayexpress my formula as follows:

0 CH: L(%CH2I:CH3 CI Among the preferable compounds are also thepeptones acylated with fatty acids of higher molecular weight, such asstearyl peptone, for example.

While I have not set forth in detail the compounds covered by thespecific formula set out above, those skilled in the art will readilyunderstand from the manner in which the formula is expressed which ofthe compounds shown in the tables are covered by such formula, togetherwith additional compounds not disclosed which may be produced inaccordance with the invention and function satisfactorily asanti-spatterers.

As to the specific application of the invention to margarine or otheremulsions and oleaginous culinary emulsions, it is clear that there aremany nitrogenous compounds devoid of the linkage described containingbalanced hydrophile and lipophile groups. It is impractical andunnecessary to list each particular combination which can be used inaccordance with my invention. Moreover, while I leave something to theskill of persons applying my invention, the description is sufficientlyexhaustive, particularly when considered with respect to the priorapplications, to enable those skilled in the art successfully topractice the same.

The term non-spatteriug margarine as used in the claims is em loyed todesignate a margarine, the frying .havior of which is improved by theaddition thereto of the novel materials of my invention hereindescribed. The term margarine" includes all forms of margarine type ofemulsions intended for culinary and table use, either containing animalor vegetable fats, and either churned with cultured milk, sweet milk,water or other types of oleaginous material. Examples of margarinewithin the meaning of the term, in addition to the usual margarine ofcommerce, are pufl' paste, renovated butter, and any like fatty-aqueouscomposition which may be used in frying.

Vl'hat I claim as new and desire to protect by Letters Patent of theUnited States is:

1. A non-spattering margarine having aqueous and oleaginous media, andhaving included therein a proportion of a nitrogenous substancerepresented by the formula wherein F and O are carbon and oxygen,respectively. L' is the lipophile radicle with more than 18 carbon atomsin the form of an alkyl or alkoxy group, or a derivative of an alkyl oralkoxy group and R represents a balancing nitrogenous hydrophile groupdevoid of the linkage wherein 0" represents oxygen; X stands forphosphorous or sulphur in the form of their oxygenated acid radicals; Crepresents carbon; H is hydrogen; w is a small whole number; and N istrivalent or pentavalent nitrogen, the terminal oxygen indicated beingdirectly linked to carbon.

2. A non-spattering margarine having aqueous and oleaginous media, andhaving included therein a proportion of a nitrogenous substancerepresented by the formula wherein C and O are carbon and oxygen,respectively, L is the lipophile radicle with more than 18 carbon atomsin the form of an alkyl group of higher molecular weight and Rrepresents a balancing nitrogenous hydrophile group devoid of thelinkage wherein 0 represents oxygen; X stands for phosphorous or sulphurin the form of their oxygenated acid radicals; C represents carbon; H ish drogen; w is a small whole number; an N is trivalent or pentavalentnitrogen, the terminal oxygen indicated being directly linked to carbon.

3. A non-spattering margarine having aqueous and oleaginous media, andhaving included therein a proportion of a nitrogenous substancerepresented by the formula wherein C and O are carbon and oxygen,respectively, L is a lipophile group with more than eighteen carbonatoms and R is a balancing betaine radicle devoid of the linkage h i C,O, H, N a d C1 r p resent carbon, oxygen, hydrogen, nitrogen andchlorine respectively and L is a balancing lipophile group with morethan 18 carbon atoms.

In witness whereof I hereunto subscribe my name this 8th day of August,1930.

BENJAltflN R. HARRIS.

